Catalysis Surveys from Japan 3 (1999) 55–60 55

A new process for acetic acid production by direct oxidation of

ethylene
Ken-ichi Sano a , Hiroshi Uchida b and Syoichirou Wakabayashi b
a Catalysis Section, Central Research Laboratory, Showa Denko K.K., 5-1 Ogimachi, Kawasaki, Kanagawa 210-0867, Japan
b Technology and Development Department, Oita Works, Showa Denko K.K., 2 Nakanosu, Oita 870-0189, Japan

A new process for acetic acid production by direct oxidation of ethylene which was established and commercialized is described.
The catalyst system consisting of Pd and heteropoly acid exhibits excellent activity and selectivity. The addition of Se or Te to the
catalyst system is effective to suppress the formation of carbon dioxide. This new process is applicable to a plant of a wide range of
size corresponding to the local demand. Because this new process produces little waste water, it is very friendly to the environment.
Keywords: acetic acid, oxidation, Pd, heteropoly acid, ethylene

1. Background [1] 1.2. Uses of acetic acid

1.1. A short history of acetic acid manufacturing Acetic acid has the demand of about 5.4 million
tons/year in the world in 1997. It is used in vinyl acetate,
technologies
solvent for production of pure terephthalic acid (PTA),
acetic anhydride, acetates, and others, as shown in ta-
Among the organic compounds, acetic acid has been
ble 1 [2].
very familiar to mankind since it has been used as vinegar
for a long time. Vinegar was produced by alcohol fermen-
tation before Christ, and even now this brewing method is 2. Industrial manufacturing process [1]
used for vinegar production.
As the demand for acetic acid grew in a wide range 2.1. Methanol carbonylation process
of fields, pyroligneous acid, which is produced by the dry
This process, which is called Monsanto process, uses
distillation of wood, and used by alchemists in medieval
methanol and carbon monoxide as the raw materials to syn-
Europe, became a world-wide manufacturing process un-
thesize acetic acid. Because the price of naphtha has risen
til the middle of the 20th century. This pyroligneous acid
and the relatively cheap methanol, produced from off gas,
method was replaced by synthetic processes and is scarcely natural gas, and so on, has been available after the oil cri-
used now. In 1914, the acetaldehyde oxidation process was sis, this process has rapidly become prevalent. At present,
industrialized in Germany. Acetaldehyde was synthesized this process accounts for 60% of the production capacity of
by hydration of acetylene produced from carbide at that the world.
time. The epoch-making process, the so-called Hoechst-
Wacker process which uses ethylene as the raw material,
was developed in 1959. The conventional process for the CH3 OH + CO → CH3 COOH (1)
preparation of acetaldehyde from acetylene was mostly re- In the Monsanto process, the selectivities to acetic acid
placed by this process. At the same period, the technology based on methanol and carbon monoxide are 99% and 90%,
of hydrocarbon oxidation made progress. Then oxidation respectively, when rhodium is used as a catalyst and iodine
of n-butane in liquid phase to produce acetic acid was in- as an activator. These days, most of the methanol carbony-
dustrialized in 1952, and liquid phase oxidation of naphtha lation processes have adopted this catalyst system.
to produce acetic acid was commercialized in 1956.
Table 1
In the mean time, the manufacturing process of acetic Demand for acetic acid by applications (1,000 t/y).
acid by the carbonylation of methanol was developed. This
1995 1997
process uses methanol and carbon monoxide as raw ma-
terials which are produced from natural gas, coal, heavy Vinyl acetate monomer 1,812 1,996
residual oil, and others. BASF (Germany) industrialized Acetic anhydride 713 743
PTA 727 955
this process in 1960, and Monsanto (USA) industrialized it Acetates 636 661
in 1970. Especially the latter process, known as Monsanto Others 1,036 1,030
process, has become the dominant industrial route for acetic Total 4,924 5,385
acid manufacturing.

 Baltzer Science Publishers BV

56 K.-i. Sano et al. / Acetic acid production by direct oxidation of ethylene
Figure 1. Process flowsheet of Monsanto’s acetic acid process.
The flowsheet is shown in figure 1 [3]. Methanol and
carbon monoxide are supplied continuously into the reac-
tor. The exhaust gas from the reaction section, together
with exhaust gas from the purification section, are washed
in the scrubber, then the light-ends are recovered and recy-
cled to the reaction section. On the other hand, the reaction
product (crude acetic acid) is sent to the light-ends column,
and acetic acid is taken out as a side-cut. The overhead and
the bottoms including the catalyst are returned to the reac-
tion section. Side-cut acetic acid is sent to the dehydration
column, then the mixture of water and acetic acid is taken
out from the top, and returned to the reaction section. The
bottoms of the dehydration column are sent to the subse-
quent product column. A small amount of the heavy-ends,
which contain propionic acid, is taken out from its bottom.
The overhead is further purified in the next fractionation
column, and purified acetic acid is obtained as a side-cut.
The overhead and the bottoms of the fractionation column
are recycled into the reaction section.
2.2. Acetaldehyde oxidation process
First, ethylene is oxidized into acetaldehyde with a
PdCl2 –CuCl2 catalyst, which is subsequently oxidized to
acetic acid with a manganese acetate catalyst. This process
was prevalent before the appearance of the methanol car-
bonylation process. At present, however, the share of this
process has fallen to 22% of the world production.
C2 H4 + (1/2)O2 → CH3 CHO
CH3 CHO + (1/2)O2 → CH3 COOH
The flowsheet of this process is shown in figures 2 and
3 [4]. Acetaldehyde vapor produced in the reactor leaves
the gas-liquid separator together with water vapor and un-
reacted gases. After cooling, acetaldehyde is absorbed with
water and the remaining gas is recycled to the reactor. The
light-ends are removed at the light-ends column. Next, by-
products, such as methyl acetate and crotonaldehyde, are
removed as a side-cut from the product column. Further-
more, by-product acetic acid, together with water, is re-
moved from the bottom, and acetaldehyde is obtained from
the top.
In the oxidation process to acetic acid, acetaldehyde is
supplied near the top of the reactor and oxidized with the
rising oxygen gas introduced from the bottom. The liq-
uid reaction product, which is taken out from the reactor,
contains by-products, such as formic acid, methyl acetate,
ethylidene diacetate and others as well as a small amount
of unreacted acetaldehyde, water, and catalyst. Thus, the
light-ends are removed and the catalyst is recovered in the
purification section. The heavy-ends are removed from the
bottom of the fractionation column, then purified acetic acid
is obtained. Acetic acid contained in the bottoms of the
fractionation column is recovered at the recovery column,
and the heavy-ends are removed. The recovered catalyst is
recycled.
2.3. Hydrocarbon (butane, naphtha) oxidation process
Hydrocarbons, such as butane and naphtha, are oxidized
directly into acetic acid, and 9% of the world’s production
capacity owes this process. Acetate catalysts, for exam-
ple, cobalt acetate and manganese acetate, are used. Since
this method uses hydrocarbons with high numbers of car-
bon atom as raw materials, not only acetic acid but acetone,
formic acid, propionic acid, and others are coproduced. Ac-
cordingly, the yield of acetic acid is much lower than those
of the other processes, but this process has advantages when
(2) manufacturing various acids simultaneously is desired.
(3)
3. Direct oxidation of ethylene. A new Showa Denko
K.K. process
Showa Denko K.K. has developed a one-stage process
of acetic acid production by direct oxidation of ethylene.
In this process, acetic acid is manufactured with high
selectivity from a mixture of ethylene and oxygen in the
vapor-phase at 160–210 ◦ C over a solid catalyst. The main
 K.-i. Sano et al. / Acetic acid production by direct oxidation of ethylene
Figure 2. Process flowsheet of ethylene oxidation to acetaldehyde.
Figure 3. Process flowsheet of acetaldehyde oxidation to acetic acid.
reaction for acetic acid is shown below, together with the
major side-reactions, which are the combustion of ethylene
and the production of acetaldehyde.
In addition, small amounts of several compounds with
low and high boiling points are formed.
A great amount of heat is generated in this reaction, and
it is recovered as steam which is used for the heat source
in the purification section.
(Main reaction) C2 H4 + O2 → CH3 COOH (4)
(Side reactions) C2 H4 + 3O2 → 2CO2 + 2H2 O (5)
C2 H4 + (1/2)O2 → CH3 CHO (2)
The flowsheet of this process is shown in figure 4. The
product gas from the reactor is cooled to ambient temper-
ature. Thereby the reaction products such as acetic acid,
organic by-products, and water are condensed and are sep-
arated from un-condensed gas. The condensate is pulled
out of the reaction section and led to the crude acetic acid
tank which is connected to the purification section. The
un-condensed gas is recycled to the reactor after it is pres-
surized by the compressor.
The crude acetic acid stored in the crude acetic acid
tank is sent to the light-ends column. In this column, the
light-end by-products, such as acetaldehyde, ethyl acetate,
ethanol, and others, are removed from acetic acid by dis-
tillation. Then water is separated by extraction.
57
The acetic acid, free from water and the light-ends,
is sent to the final purification section. In this section,
both trace amounts of impurities and the heavy-ends are
removed, and highly pure acetic acid is obtained as the
product.
The chemical processes are required to be both compet-
itive and environmentally friendly: Showa Denko K.K.’s
new process meets these requirements. Usually the pu-
rification of acetic acid is very energy consuming, since a
great amount of water is used in the oxidation reaction. To
solve this problem, Showa Denko K.K. has developed an
energy saving process by combining the extraction and the
distillation operation in which water is efficiently separated
from acetic acid [5–7]. This process is also very friendly
to the environment, because it generates little waste ow-
ing to the high selectivity of the reaction. No toxic waste,
and only a small volume of waste water were produced.
Moreover, it has a great advantage since no special mate-
rial is required for the construction of plants; adequately
used stainless steel is good enough for the facilities, be-
cause the process does not treat any corrosive compounds
except for acetic acid.
Showa Denko K.K. constructed the first commercial
plant based on the new process. It has the capacity of
100,000 tons/year of acetic acid in Oita, Japan. The plant
was completed in August 1997. After the trial run, the plant
has been operated successfully since November 1997 [15].
58 K.-i. Sano et al. / Acetic acid production by direct oxidation of ethylene

Figure 4. Process flowsheet of direct oxidation to ethylene into acetic acid.

Table 2 Table 3
Proposed catalysts for direct oxidation of ethylene. Combination of Pd and heteropoly acid.a

Catalyst Temperature Pressure Selectivity STY Ref. Catalyst STYb Selectivity (%)
(◦ C) (kg/cm2 G) (%) (g/l·h) HOAcc HAcd CO2
Pd–Cr/Al2 O3 180 1 60 – [5]
Pd–H4 SiW12 O40 93.1 78.5 5.5 14.2
Pd–V2 O5 248 1 74 2 [6]
Pd–H3 PW12 O40 83.3 78.0 5.0 16.0
Pd–V2 O5 –Sb2 O5 /Al2 O3 250 1 84 27 [7]
Pd–H4 SiMo6 W6 O40 91.2 77.6 4.4 17.5
Pd–H3 PO4 /SiO2 150 1 90 56 [8]
Pd–H3 PMo6 W6 O40 75.1 76.5 4.1 19.2
Pd–Au–H2 SO4 /active carbon 150 3.4 85 107 [9] Pd–H3 PMo12 O40 68.5 77.5 4.6 17.8
Pd–Ga0.05 H3.85 SiW12 O40 90.4 80.1 4.1 15.6
Pd–Mg0.05 H3.9 SiW12 O40 90.8 79.7 5.5 14.6
4. Catalyst development for the direct oxidation Pd–Ga0.05 H2.85 PW12 O40 75.6 74.8 3.2 21.8
Pd–Li0.05 H3.95 SiW12 O40 91.0 79.9 3.9 16.1
process Pd–Cu0.05 H3.9 SiW12 O40 90.9 78.6 4.9 16.4
Pd 0 0 0 100
Several catalyst systems were proposed in the past for H3 PW12 O40 0 0 0 0
the direct oxidation of ethylene to acetic acid, as shown Pd–H5 PMo10 V2 O40 94.0 61.4 19.4 17.6
in table 2, for example. However, these catalysts have a Reaction conditions: reaction pressure = 5 kg/cm2 G; reaction
not exhibited satisfactory performance for the industrial- temperature = 150 ◦ C; GHSV = 3,000/h; gas component (C2 H4 /O2 /
scale production of acetic acid. Here it is noteworthy that H2 O/inert gas = 50/7/30/13).
b STY = space time yield (g/l-catalyst·h).
acetic acid is obtained with relatively high selectivity by c HOAc = acetic acid.
the combination of Pd metal and acid catalysts. d HAc = acetaldehyde.

4.1. Reaction mechanism V2 O5 , or Pd–V2 O5 –Sb2 O5 /Al2 O3 shown in table 2, mainly

The following two reaction schemes may be considered
for the direct oxidation of ethylene to acetic acid. One
is the route where ethanol is formed by the hydration of
ethylene and then it is oxidized to acetic acid. In this
route, if the ethanol formed is irreversibly oxidized into
acetic acid, these reactions can to proceed under relatively
moderate conditions. It is considered that with catalysts
Pd–H3 PO4 /SiO2 and Pd–Au–H2SO4 /active carbon shown
in table 2, the reaction mainly proceeds by this mecha-
nism.
follow this mechanism.
C2 H4 + (1/2)O2 → CH3 CHO (2)
CH3 CHO + (1/2)O2 → CH3 COOH (3)
In spite of extensive efforts based on the second route,
any industrially promising results have not been obtained.
On the other hand, the first route, via ethanol intermedi-
ate, has at least a high selectivity. Showa Denko K.K.,
therefore, has chosen the R&D strategy based on the first
reaction mechanism, and has made efforts for the improve-
ment of catalyst performance.

C2 H4 + H2 O  CH3 CH2 OH (6) 4.2. Catalyst systems consisting of Pd and heteropoly

CH3 CH2 OH + O2 → CH3 COOH + H2 O (7) acids

The other is the route where ethylene is first converted
into acetaldehyde by the Wacker type reaction, and the ac-
etaldehyde is oxidized into acetic acid. It is considered that
Pd2+ basically acts as active species, and consequently the
reoxidation of Pd is necessary to achieve the catalytic reac-
tion. The catalyst systems, for example, Pd–Cr/Al2 O3 , Pd–
We found that even a simple combination of Pd and a
heteropoly acid shows a relatively high yield of acetic acid,
as shown in table 3 [13].
When only Pd was supported on silica, no partial oxida-
tion products of ethylene were obtained, and only carbon
dioxide, a deep oxidation product, was generated. On the
 K.-i. Sano et al. / Acetic acid production by direct oxidation of ethylene 59

Table 4
other hand, a catalyst containing only tungstosilicic acid on
The effect of additional metals.a
silica gave no oxidation product except for a small amount
Catalyst STYb Selectivity (%)
of ethanol.
When the Pd salt of heteropoly acid was used as a cat- HOAcc HAcd CO2
alyst, acetaldehyde was produced as much as acetic acid. Pd–H4 SiW12 O40 93.1 78.5 5.5 14.2
It is considered that the oxidation reaction of the Wacker Pd–Se(0.02)–H4 SiW12 O40 240 86.4 8.1 5.1
Pd–Te(0.05)–H4 SiW12 O40 200 85.5 8.9 5.2
type proceeds preferentially because palladium exists in the
Pd–Sb(0.05)–H4 SiW12 O40 150 80.0 9.8 10.1
form of Pd2+ , and that acetaldehyde formed initially is fur- Pd–Bi(0.02)–H4 SiW12 O40 155 80.2 8.8 10.6
ther oxidized into acetic acid. It is not clear whether the Pd–Sn(0.1)–H4 SiW12 O40 140 79.6 5.8 14.4
oxidation of acetaldehyde into acetic acid occurs due to Pd–Ag(0.1)–H4 SiW12 O40 132 78.4 5.9 15.0
the oxidation ability of heteropoly acid or of metallic Pd Pd–Cr(0.05)–H4 SiW12 O40 97 72.2 0.9 25.6
Pd–Zn(0.05)–H4 SiW12 O40 94 70.6 1.1 27.8
which is generated during reaction by the reduction with
a Reaction conditions: reaction pressure = 5 kg/cm2 G; reaction
ethylene.
It was also found that heteropoly acids with stronger temperature = 150 ◦ C; GHSV = 3,000/h; gas component (C2 H4 /O2 /
H2 O/inert gas = 50/7/30/13).
acidity tended to show higher catalytic efficiency. A salt of b STY = space time yield (g/l-catalyst·h).
a heteropoly acid and mixed coordinated heteropoly acid, c HOAc = acetic acid.
d HAc = acetaldehyde.
having weaker acidity, showed a rather low catalytic activ-
ity, but extended the life of the catalyst.
These studies show that the combination of metallic Pd 4.4. Typical procedure of catalyst preparation and
and heteropoly acid is promising and there is a possibil- evaluation
ity of obtaining an excellent catalytic activity, after further
improvements. The typical procedure of the catalyst preparation and
the evaluation of catalyst performance are briefly described
below.
In an aqueous solution containing 10 g of sodium tetra-
4.3. Effects of the addition of the second metal component
chloropalladate(II), 250 ml of a silica carrier of 5 mm par-
ticle size was placed to absorb the entire solution. The
In the partial oxidation of hydrocarbons, carbon dioxide resultant carrier containing Pd salt was added into 200 ml
formation is always a serious problem and its suppression of an aqueous solution containing 18 g of sodium metasil-
is desirable. In this direct oxidation of ethylene, a large icate, and allowed to stand still for 20 h.
amount of carbon dioxide was formed when the catalyst of Thereafter, 10 ml of 85% aqueous hydrazine was added
a simple combination of Pd and heteropoly acid was used, to the mixture to reduce sodium tetrachloropalladate(II) to
and the oxidation to carbon dioxide based on ethylene did metallic Pd, and the resultant solid was washed with water
not drop below 10%. and dried at 110 ◦ C for 4 h. The carrier containing metallic
The formation of carbon dioxide causes not only loss Pd was then added to 90 ml of an aqueous solution con-
of ethylene but also a problem concerning large quanti- taining silicotungstic acid of which the amount was 20%
ties of heat to be removed. Moreover, because the oxygen weight of the carrier to absorb the entire solution, and dried
supplied into the feed must be controlled below the explo- at 110 ◦ C for 4 h.
sion limit, when oxygen is consumed for the undesirable 15 ml of the resultant catalyst was filled in a tubular
carbon dioxide formation, the production of acetic acid de- reactor, and a gas mixture of ethylene, oxygen, steam and
creases. nitrogen was introduced thereinto at 150 ◦ C and a pressure
For the suppression of deep oxidation and for the im- of 5 kg/cm2G. The outlet gas was cooled, and the condensed
provement of space time yield of acetic acid, the addition of liquid was collected and analyzed by gas chromatography.
a second metal component to the catalyst system consisting
of Pd and heteropoly acid was examined. The results are
5. The predominant advantages of the new process of
shown in table 4 [13]. The addition of Se, Te, Sb, Bi or
acetic acid production
Sn to the catalyst system was particularly effective to de-
crease the formation of carbon dioxide. Moreover, because In the following the advantages of the new process are
the oxygen which had been consumed for the formation of compared with the methanol carbonylation process and the
carbon dioxide was more utilized for the acetic acid for- acetaldehyde oxidation process.
mation, the catalytic activity for the acetic acid formation
increased. 5.1. Comparison with methanol carbonylation process
The catalyst with much better performance (activity, se-
lectivity and life) was obtained by the proper combination Expensive metallic materials like Hastelloy containing
of various additional metals, and the cost performance was nickel must be used in the process of methanol carbony-
improved by selecting suitable reaction conditions [14]. lation, due to the highly corrosive catalyst. The facility
60 K.-i. Sano et al. / Acetic acid production by direct oxidation of ethylene
of carbon monoxide production is also necessary. Conse-
quently the process requires heavy investments in facility
and is hardly profitable unless the production capacity is
equal to or more than 200,000 tons/year. On the other hand,
Showa Denko K.K.’s new process becomes profitable even
in the case of middle-scale facilities such as about 100,000
tons/year, and the investment can be substantially reduced
as compared with the methanol carbonylation process of
the same capacity. Since the new process is applicable to
a plant of a widely variable size, corresponding to the lo-
cal demand, the plant can be placed near the market. The
variable cost of acetic acid production depends mainly on
the price of methanol or ethylene in each case.
5.2. Comparison with acetaldehyde oxidation process
In the acetaldehyde oxidation process, the reaction is
two-staged, and many kinds of by-products complicate the
purification process. The acetaldehyde production needs
rubber and bricks for the materials of the reactor, because
aqueous hydrochloric acid is used. For these reasons, the
facility cost of the acetaldehyde oxidation process becomes
high. With the new process, the facility cost can be reduced
to 60–70% for the same production capacity. Moreover, a
great amount of water is required for the acetaldehyde pro-
duction. This means that a large-scale facility becomes
necessary to treat the waste water. On the other hand, the
waste water from the new process is about 1/15 of that
from the acetaldehyde oxidation process. The new process
is in this respect much more friendly to the environment.
Although the selectivity of each step is high in the acetalde-
hyde oxidation process, the overall selectivity of two-stage
oxidation is inferior to that of the new process. As a re-
sult, the unit consumption of ethylene of this new process
is better than that of the acetaldehyde oxidation process.
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